EP0904149A1 - Dispositif de soutirage des solides et de controle du debit des solides - Google Patents
Dispositif de soutirage des solides et de controle du debit des solidesInfo
- Publication number
- EP0904149A1 EP0904149A1 EP97929354A EP97929354A EP0904149A1 EP 0904149 A1 EP0904149 A1 EP 0904149A1 EP 97929354 A EP97929354 A EP 97929354A EP 97929354 A EP97929354 A EP 97929354A EP 0904149 A1 EP0904149 A1 EP 0904149A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid
- solids
- solid
- column
- metering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/02—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor with moving adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/10—Ion-exchange processes in general; Apparatus therefor with moving ion-exchange material; with ion-exchange material in suspension or in fluidised-bed form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/0025—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by an ascending fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/0035—Periodical feeding or evacuation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2215/00—Separating processes involving the treatment of liquids with adsorbents
- B01D2215/02—Separating processes involving the treatment of liquids with adsorbents with moving adsorbents
- B01D2215/021—Physically moving or fluidising the adsorbent beads or particles or slurry, excluding the movement of the entire columns
Definitions
- the present invention relates to a device for withdrawing solids which also makes it possible to control the flow rate of solids which applies more particularly to apparatus, devices and apparatus for continuously contacting a solid and a liquid, in particular to columns moving bed and fluidized bed.
- the invention also relates to the installation for continuously contacting a solid and a liquid comprising such a withdrawal device and an apparatus for continuously contacting a solid and a liquid.
- the solids can be in particular mineral or organic compounds, for example solid ion exchangers such as ion exchange resins or zeolites and others, generally being in the form for example of grains or beads.
- solid ion exchangers such as ion exchange resins or zeolites and others, generally being in the form for example of grains or beads.
- the most commonly used technique is that of the "fixed bed" which has been used in particular to extract compounds present in low content, as is the case in particular for demineralization of water.
- This technique consists in passing the liquid through the solids which are in the form of a fixed bed of grains contained in a column.
- the liquids, in particular the solutions to be treated are circulated through these beds of solid which are charged as and when the passages of liquids to be treated.
- Such a technique has, inter alia, the disadvantage of being applicable only if the liquid to be treated is perfectly clear because, in fact, if the latter contains solid particles in suspension, as is the case in particular for a pulp , these are stopped by the grains and cause, in the more or less long term, a clogging of the bed.
- the document GB-A-947 166 and the document FR-A-1 176 525 likewise describe tubular columns in which the granular solid material circulates from the top to the bottom of the column against the current of the liquid introduced at the base of the column, then this solid maceration is drawn off at the base of the column by means of a discharge orifice, a perforated plate, and an extraction member, for example a valve rotary.
- EP-A-0 060 207 relates to a method and to a device operating in a completely continuous manner for the extraction of ions from a clear liquid or containing suspended matter by contact with a bed of grains. exchangers.
- the device described in this document comprises a fluidization column which does not include any tray or grid capable of hindering the grading by density of the grains as a function of their ion charge, under the action of cyclic pulses generated by a pulsation generator operating by sampling at the top of the column and reinjection by jerks at the base of the column; such a device has as a major drawback the use of a valve for withdrawing the grains resulting in random control of this withdrawal and a significant risk of clogging.
- the object of the present invention is therefore to provide a device for withdrawing solids which overcomes the drawbacks of the devices of the prior art, that is to say a device which can be used continuously, which does not require the presence of neither trays nor grids and which, when the solid phase is in the form of particles or grains, does not cause any clogging, abrasion, wear and grain entrainment phenomena
- the aim of the present invention is also to provide a device which is easy to implement, easy to service and maintain, of minimum complexity, having a processing capacity equal to, or even greater than, that of the existing racking devices and making it possible to control the quantity of solid withdrawn from the column
- a device is, according to the invention, preferably applied to a column with a “moving bed” or a fluidized bed in which the solids circulate against the current of the liquids under the gravity action, but it can also be applied to any device, device, equipment or appliance in which it is necessary to implement such a device for withdrawing solids, that is to say to any device in which solids accumulate, for example it can be applied to any apparatus, device, equipment or device for treatment or bringing a liquid phase into contact with a solid or a solid with a liquid phase, such an apparatus preferably operating continuously.
- the apparatus, device or other to which the drawing-off device according to the invention is applied is generally designated by the term column, but it is obvious that this apparatus can take on a any shape and size which can be readily determined by one skilled in the art.
- the withdrawal device for apparatus in which solids are accumulated comprises withdrawal means intended to withdraw in a cyclic and controlled manner the solids accumulated in an apparatus, in particular it may be the solids collected by gravity in a column, generally at its lowest point, means for generating a flow or current of liquid under the action of a hydraulic imbalance for transferring / transporting, essentially by suction, into a working fluid, the solids collected from the device, for example the device for contacting a solid and a liquid such as a column to dosing means (also called capacity or dosing zone), by means of withdrawal means , and finally transfer means for hydraulically and sequentially transferring the solid into the working fluid generally in the form of a solid suspension, from the metering means to solid-liquid separation means.
- withdrawal means intended to withdraw in a cyclic and controlled manner the solids accumulated in an apparatus, in particular it may be the solids collected by gravity in a column, generally at its lowest point, means for generating a flow or current of liquid under the action of a hydraulic imbalance for
- Such a device does not have the drawbacks of the prior art because, in particular, that it does not have a disc, a grid or a plate, that the number of moving mechanical parts, inducing pressure losses is very small. even non-existent.
- This device is extremely simple because it does not use any complex transfer device, since the transfer of solids is essentially induced by a modification of the hydraulic balance.
- the supply of liquid to the device in which solids accumulate in particular to the device for bringing a solid and a liquid into contact, such as a column, is permanently maintained and does not undergo any interruption during withdrawal, which results in a significant increase in the effective treatment capacity of the column and allows continuous operation with a single column.
- the solids are preferably in the form of particles such as grains, granules or beads and are generally of an average size of 0.2 mm to 2 mm.
- the solids preferably consist of materials generally used in apparatuses for bringing liquid and solid into contact: they may be mineral or organic compounds, for example solid ion exchangers such as exchange resins of ions or zeolites and other divided solids
- the liquid may be any liquid capable of undergoing a liquid-solid exchange operation, it may for example be an aqueous liquid such as an aqueous effluent from various industrial operations (for example rinsing of installations), or resulting from nuclear installations (such as reprocessing factories, power stations, laboratories) ....
- the liquid is charged with various elements, for example in suspension or in solution, which one wishes to eliminate or separate by the contacting operation.
- These elements to be eliminated, or to be separated can for example be in the form of salts of various cations, in particular of metal cations, in particular of radioelements such as cesium, strontium and others, but they can also be anions or organic complexes.
- the concentration of these elements can be very variable: from the trace state (ppb) to concentrated solutions (a few tens of g / 1).
- the salts of the radioactive cations mentioned above it is generally from 0.01 to 1000 mg / 1.
- drawing off operation is generally carried out under normal conditions of temperature and pressure, but it is obvious that other temperatures and pressures can be used.
- the withdrawal means can take any suitable form known to those skilled in the art, but they generally comprise a pipe, tubing, pipe or other conduit which connects on the one hand the device in which solids are accumulated, in particular the apparatus for contacting a solid and a liquid such as a column, and on the other hand the metering means.
- the withdrawal means are connected to the apparatus in which solids have accumulated, in particular to the apparatus for bringing a solid and a liquid into contact at the point of this apparatus, or the solids in particular have accumulated. from this device where the solids are collected by gravity, that is to say essentially at the low point of the apparatus for contacting a solid and a liquid such as a column.
- the withdrawal means can for example penetrate obliquely into the apparatus such as the column and be directed towards the bottom of the said apparatus of the said column and the accumulated solids, for example by gravity, can be removed via a calibrated orifice, but such an arrangement is given only by way of illustration; the withdrawal means can of course be adapted according to the desired application and the device to which they must be connected or connected.
- the introduction, for example injection, of the working fluid into the system does not disturb the flows which take place inside of the apparatus in which the solids accumulate, in particular of the apparatus for contacting a solid and a liquid such as a column.
- the withdrawal means connecting the device such as a column to the metering means (at the metering capacity) and which are, as already described above, for example in the form of a pipe or a suction pipe, are preferably made in such a way that their pressure drop is greater than that necessary to carry out the transfer of the solids generally being in the form of a solid suspension.
- the metering means or measuring means generally take the form of a "capacity metering ", namely for example an essentially vertical tubing or pipe generally calibrated, thus making it possible to precisely measure the quantity of solids - generally in the form of a suspension of solids - withdrawn into the apparatus in which s accumulate solids such as a column.It is obvious that these metering or measuring means can be in any form for metering or measuring the solids sampled and ensuring precise control of the flow of solids.
- the means for generating a flow or current of liquid, under the action of a hydraulic imbalance, and for transporting, essentially by suction, in a working fluid, the solids collected from the apparatus in which the solids accumulate, in particular from the apparatus for bringing a solid and a liquid such as a column into contact with the metering means, by means of the withdrawal means comprise, in a first embodiment, a circuit for bypass also called “by-pass” circuit placed on the metering means, and provided with sealing means consisting for example of a "by-pass” valve.
- This "bypass" circuit preferably connects, on the one hand the metering means, and on the other hand the transfer means to the solid-liquid separation means.
- the collection of solids is therefore carried out in this embodiment by creating between the point ⁇ e the apparatus such as the contacting apparatus, where the solids are collected and collected, essentially under the action of gravity (by example the bottom of the column) and the metering means (capacity or metering area) a liquid stream or stream, by opening the sealing means such as the "by-pass" valve of the "by-pass” circuit preferably connecting the metering means and the transfer means to the solid-liquid separation means, thereby inducing a hydraulic imbalance.
- the part of the transfer means or terminates the "by-pass" circuit preferably comprises a pipe, tubing or essentially vertical descending pipe or any other known means allowing the delivery of a fluid.
- the current or flow of liquid can be obtained by placing the bypass circuit at a point located on the metering means, at a level lower, preferably significantly lower, than the level of the liquid in the device, a know at the level of the liquid leaving the top of the device, for example the contacting device of a solid and a liquid such as a column. This liquid leaves for example in a conventional manner via a weir.
- the "by-pass" bypass system comprising closure means such as a valve, and allowing the withdrawal of solids in the apparatus where solids accumulate such as a column, can advantageously be replaced by a so-called "air-lift" device placed on the metering means.
- this so-called "air-lift” device is to empty the liquid present in the upper part of the metering means (metering capacity), which creates a hydraulic imbalance, which tends to be compensated by a liquid flow or current, coming from the point (in general at a low point) of the apparatus where solids accumulate, for example from the setting apparatus contact of a solid and a liquid, or are collected, accumulates the solids generally by gravity, this flow or current of fluid being preferably directed towards the means or the metering capacity.
- Said flow or current makes it possible as 0 previously with the bypass system to draw off the solid phase at the point of the apparatus, for example from the apparatus for bringing a solid and a liquid into contact. , where solids are accumulated and collected, in particular by gravity, namely at the foot of the:> column.
- the "air lift" device is placed on the metering means at a point situated at a lower level, preferably markedly lower than the level of the liquid in the device, namely at the level of the liquid coming out from the top of the device.
- a point situated at a lower level preferably markedly lower than the level of the liquid in the device, namely at the level of the liquid coming out from the top of the device.
- the means for generating a flow or current of liquid under the action of a hydraulic imbalance, for transferring into a D driving fluid the solids from the device in which the solids are accumulated towards the metering means are not limited to the two embodiments indicated above, but can on the contrary be constituted by any other means making it possible to create a 0 hydraulic imbalance between the apparatus in which solids are accumulated such as in a column, and the metering means, in particular the metering capacity
- the withdrawal is cyclic and controlled, that is to say that the means for generating a flow or current of liquid under the action of a hydraulic imbalance are actuated at regular intervals, for example every hour. for a predetermined time, for example one to 5 minutes.
- the actuation of these means consists, for example, in putting the air lift into operation or in opening the shutter means of the "bypass" bypass system.
- the withdrawal is controlled, that is to say that when the quantity of solids desired to be withdrawn is reached, the means for generating a flow or current of liquid are ceased to operate and the transfer procedure is initiated by the means of transfer described below.
- the transfer means for hydraulically and sequentially transferring the solid into the working fluid, generally in the form of a solid suspension from the metering means to the solid-liquid separation means preferably essentially comprise means for introduction, injection of a current or flow of working fluid into the metering or measuring means (capacity or area).
- These means may for example include a tapping into which opens a pipe or tubing supplied with working fluid by a working fluid circuit provided with regulation and control means such as a valve with controlled opening making it possible to regulate the flow, the number, the timing ... of the injections of engine fluid and thus obtain an effectively sequential transfer.
- the working fluid can be any fluid suitable for such a use, but it is advantageously constituted by the liquid circulating in the apparatus where solids accumulate, in particular in the apparatus for continuously contacting a solid and of a liquid such as a column.
- the transfer means also include load breaking means conventionally constituted by a tank, also called "load breaking pot”. These load breaking means or “load breaking pot” are preferably located at a point the level of which ("altitude") is determined by balancing the pressure losses which occur in the apparatus in which solids accumulate, in particular in the apparatus for contacting a solid and a liquid such as a column, for example, in the bed of solids which is in such a column.
- the transfer means further comprise routing means comprising for example pipes, tubes, etc. connecting for example the metering means and the load breaking means, and the load breaking means and the solid-liquid separation means.
- these conveying means can be easily determined by a person skilled in the art, for example the metering means and the load breaking means can be connected by an essentially vertical ascending pipe, then by a bent pipe and finally by an essentially horizontal pipe terminating in the load-breaking "pot”; load breaking means (load-breaking "pot”) and the liquid-solid separation means can be connected by an essentially vertical downward pipe preferably starting from the bottom of the load-breaking means and ending in the liquid-solid separation means.
- Said downward pipe is preferably substantially parallel to the metering and measuring means and to the vertical upward pipe mentioned above, and is connected in the first embodiment of the invention, to the metering means by the "by -pass "preferably preferably essentially horizontally.
- Said hydraulic and sequential transfer from the metering or measuring means (capacity or metering zone) to the solid-liquid separation means therefore preferably comprises injection for a predetermined period preferably between one or a few seconds and a few minutes, for example 1 sec. 10 min. a current or flow of working fluid at a sufficient speed, preferably between 1 and 100 cm / s and in an amount sufficient to hydraulically transport the solids generally in the form of a suspension to the load breaking means or load breaking capacity and towards the separation means.
- the quantity of working fluid injected will allow the transfer of an equivalent quantity of solids (generally expressed in volume) thus forming a suspension of solids which is transferred.
- the solid-liquid separation means can comprise any device known to those skilled in the art such as a settling tank or the like allowing the separation of the solid and liquid phases.
- the device according to the invention can, in particular, but not exclusively, be applied to any apparatus, device, equipment or apparatus for continuously contacting a solid and a liquid, in particular to a moving bed or fluidized bed column and it then makes it possible to take advantage of the advantages of a fixed bed column, in particular maximum loading or unloading of the solid, maximum contact capacity, while retaining the benefits of continuous operation.
- the device according to the invention has neither tray, grid, or other device impeding the flow; no pump or other is necessary to transport and transfer the solid or the solid suspension, moreover in the case where an "air lift" system is used, the valves, taps and others can be completely deleted.
- the invention also relates to the installation comprising a device or apparatus for bringing a liquid and a solid into contact with the withdrawal device according to the invention.
- the withdrawal device is applied to the columns operating in a fluidized bed by creating a flaring in the lower part of the column in which the solids, in particular in the form of grains, come accumulate.
- the solid bed then has the behavior of a packed moving bed whose linear pressure drop is sufficient to allow the device of the invention to be used without disturbing the fluidized bed during the sequences of solid transfer. It is obvious that any means other than a flaring allowing said accumulation of solids also falls within the scope of the invention.
- FIG. 1 is a vertical section view schematically illustrating a movable bed column equipped with the withdrawal device according to the present invention
- FIG. 2 is a vertical section view schematically illustrating another embodiment of the device according to the invention applied as in FIG. 1 to a column with a moving bed, but in which the circulation of the solid is carried out by an "air-" device. lift “instead of a" by-pass “system.
- FIG. 3 is a vertical section view schematically illustrating a fluidized bed column equipped with the withdrawal device according to the present invention in the embodiment according to FIG. 2, that is to say provided with an "air-lift" device.
- FIG 1 there is shown very schematically an installation comprising a movable bed column (1) equipped with the device according to the invention.
- This device comprises a suction tube for the solids (2) penetrating obliquely into the lower part of the column (1) and oriented towards the bottom of the said column and connected to a vertical capacity (3) allowing the dosage of the solid withdrawn.
- a liquid supply pipe (4) is fixed at the low point of the metering capacity (3) which is itself connected at one point to a load breaking capacity (5)
- the load breaking capacity is equipped a tube (6) allowing the transfer of the solid-liquid suspension to a separation equipment (not shown) such as a screen, filter or other.
- a bypass pipe (7) provided with a remote-controlled valve (8) connects the metering capacity (3) to the transfer pipe (6).
- the column (1) is continuously supplied by the liquid phase at point (17).
- the liquid phase after having passed from bottom to top the solid bed leaves by overflow at point (18) do the column (1) which also has a pipe (9) for supplying the solid.
- the tubing (7) is placed so as to be located under the outlet point (18) of the liquid.
- the solid In operation, the solid is withdrawn sequentially from column (1) in the manner next.
- the remote-controlled valve (8) is open, the pipe (7) being situated at an altitude lower than that of the point of exit of the liquid (18) from the column, the liquid will tend to circulate towards the tube (2) thus creating a liquid flow whose speed is sufficient to suck the solids from the column (1) to the metering capacity (3).
- a solid level measuring device placed at (30) controls the closing of the remote-controlled valve (8). Then we introduce through the pipeline
- the device according to the invention comprises, as means for generating a flow or current of liquid allowing the circulation of solids, an "air lift" device instead of a "bypass" system.
- the withdrawal device of the present invention already shown in FIG. 2 is applied to a fluidized bed column instead of a moving bed column.
- the solid is accumulated in the flaring (10) at the bottom of the column from which it can be withdrawn using the device of the invention.
- a column with a diameter of 500 mm and a height of 7.0 m is used.
- the column contains a bed of 1.2 m J of a solid ore exchanger having a grain size of 0.8 mm capable of fixing metal salts contained in an aqueous solution
- the bed is not fluidized and occupies a height of 6.0 m column.
- the solution admitted into the column at a rate of 0.5 m 3 / h contains approximately 20 mg / 1 of metal salts.
- the grains sampled at a rate of 15 l / h contain approximately 660 mg / l of metal salts and the solution at the outlet of the column contains only 0.02 mg / l of metal salts.
- the grains are removed every hour according to the following sequence operation of the racking air-lift for 3.5 minutes, flushing for 45 seconds of 15 liters of solids using 15 liters of solution.
- the withdrawal device according to the invention allows absolutely continuous operation, at maximum capacity, without disturbing the flow inside. of the column, maintenance and upkeep being reduced to a minimum.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9607443A FR2749776B1 (fr) | 1996-06-14 | 1996-06-14 | Dispositif de soutirage des solides et de controle du debit des solides en particulier pour appareil de mise en contact en continu d'un solide et d'un liquide |
FR9607443 | 1996-06-14 | ||
PCT/FR1997/001076 WO1997047379A1 (fr) | 1996-06-14 | 1997-06-13 | Dispositif de soutirage des solides et de controle du debit des solides |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0904149A1 true EP0904149A1 (fr) | 1999-03-31 |
Family
ID=9493074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97929354A Withdrawn EP0904149A1 (fr) | 1996-06-14 | 1997-06-13 | Dispositif de soutirage des solides et de controle du debit des solides |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0904149A1 (fr) |
JP (1) | JP2000511821A (fr) |
AU (1) | AU3348397A (fr) |
FR (1) | FR2749776B1 (fr) |
SK (1) | SK170198A3 (fr) |
WO (1) | WO1997047379A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6550120B2 (ja) * | 2017-12-14 | 2019-07-24 | 四電エンジニアリング株式会社 | 粉体の振動流動層式分離装置 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2671714A (en) * | 1952-04-10 | 1954-03-09 | Dow Chemical Co | Continuous method for concentrating ions in solutions |
GB1261082A (en) * | 1969-06-09 | 1972-01-19 | Paterson Candy Internat Ltd | Continuous ion exchange apparatus and method of operating the same |
US3839197A (en) * | 1973-08-09 | 1974-10-01 | Universal Oil Prod Co | Controlled inter-reactor catalyst transport method |
US5270018A (en) * | 1984-06-12 | 1993-12-14 | Chevron Research Company | Apparatus for withdrawing a particulate solid from a packed, non-fluidized bed |
-
1996
- 1996-06-14 FR FR9607443A patent/FR2749776B1/fr not_active Expired - Lifetime
-
1997
- 1997-06-13 SK SK1701-98A patent/SK170198A3/sk unknown
- 1997-06-13 AU AU33483/97A patent/AU3348397A/en not_active Abandoned
- 1997-06-13 JP JP10501322A patent/JP2000511821A/ja active Pending
- 1997-06-13 WO PCT/FR1997/001076 patent/WO1997047379A1/fr not_active Application Discontinuation
- 1997-06-13 EP EP97929354A patent/EP0904149A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO9747379A1 * |
Also Published As
Publication number | Publication date |
---|---|
SK170198A3 (en) | 1999-12-10 |
FR2749776A1 (fr) | 1997-12-19 |
FR2749776B1 (fr) | 1998-08-07 |
AU3348397A (en) | 1998-01-07 |
JP2000511821A (ja) | 2000-09-12 |
WO1997047379A1 (fr) | 1997-12-18 |
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